Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Language: Английский

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Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(25), P. 8304 - 8329

Published: Oct. 12, 2018

Abstract In recent years, transition‐metal‐catalyzed C−H activation has become a key strategy in the field of organic synthesis. Rhodium complexes are widely used as catalysts variety functionalization reactions because their high reactivity and selectivity. The availability number rhodium various oxidation states enables diverse reaction patterns to be obtained. Regioselectivity, an important issue chemistry, can accomplished by using directing group assist reaction. However, obtain target functionalized compounds, it is also necessary use that easily removed. A wide range directed catalyzed have been reported date. this Review, we discuss Rh‐catalyzed aided removable such phenol, amine, aldehyde, ketones, ester, acid, sulfonic N‐heteroaromatic derivatives.

Language: Английский

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Recent advances in positional-selective alkenylations: removable guidance for twofold C–H activation

Organic Chemistry Frontiers, Journal Year: 2017, Volume and Issue: 4(7), P. 1435 - 1467

Published: Jan. 1, 2017

Recent advances in transition-metal catalyzed positional-selective alkenylations via twofold C–H activation directed by removable or traceless directing groups are reviewed.

Language: Английский

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Recent Advances in Catalytic C(sp²)–H Allylation Reactions

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(4), P. 2821 - 2847

Published: March 14, 2017

The linear or branched allyl moieties on aromatic rings are well-known as ubiquitous structural motifs found in a range of natural products and medicinally relevant molecules. They also represent an important class organic intermediates for the transformation olefin group into many useful functional groups. Established methods installation allylic groups rely primarily nucleophilic substitution transmetalation aryl metal complexes to electrophiles, Lewis acid-mediated Friedel–Crafts allylation electron-rich arenes, Tsuji–Trost reactions with π-allyl species. Complementing previous protocols, transition metal-catalyzed via C–H activation strategy using various surrogates like acetates, carbonates, phosphonates, halides, alcohols, vinyl oxiranes, allenes, 1,3-dienes, others have recently emerged powerful tool creating corresponding allyl, crotyl prenyl moieties. This review, which includes all reported literature until beginning 2017, focuses recent progress direct vinylic C(sp2)–H bonds sources catalysts.

Language: Английский

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Enantioselective Synthesis of C−N Axially Chiral N‐Aryloxindoles by Asymmetric Rhodium‐Catalyzed Dual C−H Activation

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(20), P. 6732 - 6736

Published: March 20, 2019

The first enantioselective Satoh-Miura-type reaction is reported. A variety of C-N axially chiral N-aryloxindoles have been enantioselectively synthesized by an asymmetric rhodium-catalyzed dual C-H activation and alkynes. High yields enantioselectivities were obtained (up to 99 % yield up ee). To date, it also the example synthesis compounds such a strategy.

Language: Английский

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Rhodium-Catalyzed [3 + 2] Annulation of Cyclic N-Acyl Ketimines with Activated Olefins: Anticancer Activity of Spiroisoindolinones

The Journal of Organic Chemistry, Journal Year: 2016, Volume and Issue: 82(7), P. 3359 - 3367

Published: Dec. 1, 2016

The rhodium(III)-catalyzed redox-neutral coupling reaction of N-acyl ketimines generated in situ from 3-hydroxyisoindolinones with various activated olefins is described. This approach leads to the synthesis bioactive spiroisoindolinone derivatives moderate high yields. In case internal such as maleimides, maleates, fumarates, and cinnamates, spiroindanes were obtained by [3 + 2] annulations reaction. sharp contrast, acrylates quinones displayed β-H elimination followed Prins-type cyclization furnishing spiroindenes. synthetic compounds evaluated for vitro anticancer activity against androgen-sensitive human prostate adenocarcinoma cells (LNCaP), (DU145), endometrial (Ishikawa), breast cancer cell (MCF-7), triple negative (MDA-MB-231). Notably, quinone-containing spiroindenes potent about 2- 3-fold stronger than that agent doxorubicin.

Language: Английский

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Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

European Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 2018(42), P. 5777 - 5794

Published: March 15, 2018

This review aims to summarize the recent advances in field of Cp*M III (Co, Rh, Ir)‐catalyzed C–H activation followed by subsequent intramolecular reaction. approach has allowed synthesis valuable heterocycles with high structural diversity and complexity, including polycyclic macrocyclic compounds. In this review, a particular attention been made nature coupling partner (alkene, alkyne, etc) its connection either aryl (or vinyl) group or directing group. Hence, different types transformation can occur, involving one two cyclizations depending on Finally, we discuss some mechanistical aspects (role external internal oxidation, account for formation cyclic structures.

Language: Английский

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Synthesis of Succinimide-Containing Chromones, Naphthoquinones, and Xanthones under Rh(III) Catalysis: Evaluation of Anticancer Activity

The Journal of Organic Chemistry, Journal Year: 2016, Volume and Issue: 81(24), P. 12416 - 12425

Published: Nov. 22, 2016

The weakly coordinating ketone group directed C–H functionalizations of chromones, 1,4-naphthoquinones, and xanthones with various maleimides under rhodium(III) catalysis are described. These protocols efficiently provide a range succinimide-containing naphthoquinones, excellent site selectivity functional compatibility. All synthetic compounds were screened for in vitro anticancer activity against human breast adenocarcinoma cell lines (MCF-7). In particular, 7aa 7ca naphthoquinone scaffold found to be highly cytotoxic, an competitive agent doxorubicin.

Language: Английский

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Recent advances in Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation via carbene migratory insertion

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(7), P. 1438 - 1458

Published: Jan. 1, 2021

The review highlighted diverse annulations, including nitrogen, oxygen, sulfur heterocycles and carbocylizations via Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation with various arene carbene precursors.

Language: Английский

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Co(III), Rh(III) & Ir(III)‐Catalyzed Direct C−H Alkylation/Alkenylation/Arylation with Carbene Precursors

Chemistry - An Asian Journal, Journal Year: 2021, Volume and Issue: 16(5), P. 443 - 459

Published: Jan. 15, 2021

Metal carbenes play a pivotal role in transition-metal-catalyzed synthetic transfer reactions. The metal carbene is generated either from diazo compound through facile extrusion of N2 with catalyst or situ other sources like triazoles, pyriodotriazoles, sulfoxonium ylides and iodonium-ylide. On the hand, Co(III), Rh(III) & Ir(III)-catalyzed C-H functionalizations have been well established as key step to enable construction various transformations. Interestingly, recent years, merging these two concepts activation migratory insertion gained much attention, particular group 9 metal-catalyzed arene precursors via insertion. In this review, we summarize advances direct alkylation/alkenylation/arylation also discuss intermediates within catalytic cycles.

Language: Английский

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